Methods of desulphurizing fluid materials

ABSTRACT

A method for desulphurizing fluid materials such as molten iron, steel, stack gases, synthetic natural gases, boiler gases, coal gasification and liquification products and the like is provided in which one of the group rare earth oxides, rare earth fluocarbonates, rare earth oxyfluorides and mixtures thereof, including bastnasite concentrates are reacted at low oxygen potential, with the sulphur to be removed to form one of the group consisting of rare earth sulphides, rare earth oxysulphides and mixtures thereof. The low oxygen potential can be achieved by carrying out the reaction in the presence of vacuum, reducing gases, carbon, etc.

This application is a continuation-in-part of our copending application Ser. No. 705,525, filed July 15, 1976, now U.S. Pat. No. 4,084,960.

This invention relates to methods of desulphurizing fluid materials and particularly to a method of external desulphurizing fluids such as molten iron and steel, stack gases, coal gases, coal liquification products, and the like using rare earth oxides, rare earth fluorocarbonates or rare earth oxyfluorides in an essentially dry process.

As we have indicated above this method is adapted to the desulphurization of essentially any fluid material. We shall, however, discuss the method in connection with the two most pressing problems of desulphurization which industry presently faces, i.e. the desulphurization of molten iron and steel baths and the desulphurization of stack gases.

External desulphurization of molten iron and steel has been practiced for quite some time. It is recognized, even necessary practice, in much of the iron and steel produced today. In current practices for desulphurization of iron and steel it is common to add magnesium metal, magcoke, calcium oxide, calcium carbide or mixtures of calcium oxide and calcium carbide as the desulphurizing agent. Unfortunately, there are serious problems, as well as major cost items involved, in the use of all of these materials for desulphurization. Obviously, both CaO and CaC₂ must be stored under dry conditions, since CaO will hydrate and CaC₂ will liberate acetylene on contact with moisture. Magnesium is, of course, highly incendiary and must be carefully stored and handled. There are also further problems associated with the disposal of spent desulphurization slags containing unreacted CaC₂.

We have found that these storage, material handling and disposal problems are markedly reduced by using rare earth oxides in a low oxygen content bath of molten iron or steel. The process is adapted to the desulphurization of pig iron or steel where carbon monoxide, evolved by the reaction, where carbon is used as a deoxidizer, is diluted with an inert gas such as nitrogen or by vacuum degassing the melt in order to reduce the oxygen potential and thereby increase the efficiency of the reaction by reducing the likelihood of forming oxysulfides. The principle may also be used for desulphurizing stack gases from boilers, etc., as we shall discuss in more detail hereafter.

In desulphurizing molten iron and steel in the practice of this invention we preferably follow the steps of reacting rare earth oxide, rare earth oxyfluorides, rare earth fluocarbonates and mixtures thereof including bastnasite concentrates in the presence of a deoxidizing agent with the sulphur to be removed to form one of the group consisting of rare earth sulphide and rare earth oxysulphide and mixtures thereof.

Preferably, hot metal is treated in a ladle or transfer car with rare earth oxides, by the simple addition and mixing of the rare earth oxides, by an injection technique in which the rare earth oxides are injected into the molten bath in a carrier gas such as argon or nitrogen or by the use of an "active lining" i.e., a rare earth oxide lining in the vessel. In any case, the chemical reactions involved are:

    2CeO.sub.2(s) + [C] = Ce.sub.2 O.sub.3(s) + CO.sub.(g) . . . (1)

    RE.sub.2 O.sub.3(s) + [C] + [S].sub.1w/o = RE.sub.2 O.sub.2 S.sub.(s) + CO.sub.(g) . .                                            (2)

and

    RE.sub.2 O.sub.2 S.sub.(s) + 2[C]+ 2[S].sub.1w/o = RE.sub.2 S.sub.3(s) + 2CO.sub.(g) . .                                           (3)

The product sulphide or oxysulphide will either be fixed in an `active` lining or removed by flotation and absorbed into the slag cover and vessel lining depending upon the process used for introducing the rare earth oxide.

The products of desulphurization of carbon saturated iron with RE oxides is dependent on the partial pressure of CO, pCO, and the Henrian sulphur activity in the metal, h_(S). Using cerium as the representative rare earth, the following standard free energy changes the equilibrium constants at 1500° C. for different desulphurization reactions can be calculated from thermodynamic data in the literature:

    __________________________________________________________________________     REACTION                  ΔG° cal.                                                                   K.sub.1773                                  __________________________________________________________________________     2CeO.sub.2(s) + [C] = Ce.sub.2 O.sub.3(s) + CO.sub.(g)                                                   66000 - 53.16T                                                                          pCO = 3041                                  Ce.sub.2 O.sub.3(s) +  [C] + [S].sub.1w/o = Ce.sub.2 O.sub.2 S.sub.(s) +       CO.sub.(g)                18220 - 26.43T                                                                          pCO/h.sub.S = 3395                          Ce.sub.2 O.sub.2 S.sub.(s) + 2[C] + 2[S].sub.1w/o = Ce.sub.2 S.sub.3(s) +      2CO.sub.(g)               66180 - 39.86T                                                                          p.sup.2 CO/h.sub.S.sup.2 = 3.6              3/2 Ce.sub.2 O.sub.2 S.sub.(s) + 3[C] + 5/2[S].sub.1w/o = Ce.sub.3             S.sub.4(s) + 3CO.sub.(g)  127050 - 72.1T                                                                          p.sup.3 CO/h.sub.S.sup.5/2 = 1.25           Ce.sub.2 O.sub.2 S.sub.(s) + 2[C] + [S].sub.1w/o = 2CeS.sub.(s) +              2CO.sub.(g)               120,860 -  61.0T                                                                        p.sup.2 CO/h.sub.S = .027                   C.sub.(s) + 1/2 O.sub.2(g) = CO.sub.(g)                                                                  -28200 - 20.16T                                                                         pCO/p.sup.1/2 O.sub.2 = 7.6 ×                                            10.sup.-7                                   1/2S.sub.2(g) = [S].sub.1w/o                                                                             -31520 + 5.27T                                                                          h.sub.S /p.sup.1/2 S.sub.2 + 5.4                                               × 10.sup.2                            __________________________________________________________________________

The thermodynamics of desulphurization with lanthanium oxide, La₂ O₃, are similar although, in this case, LaO₂ is unstable and there will be no conversion corresponding to CeO₂ → Ce₂ O₃.

In the case of desulphurization of gases, such as stack gases, assuming the following gas composition at 1000° L C.:

    ______________________________________                                         Component         Vol. %                                                       ______________________________________                                         CO.sub.2          16                                                           CO                40                                                           H.sub.2           40                                                           N.sub.2           4                                                            H.sub.2 S         0.3                                                                            (200 grains/100 ft.sup.3.)                                   ______________________________________                                    

This equilibrium gas composition is represented by point A on the diagram illustrated as FIG. 6 where CO/CO₂ = 2.5 and H₂ /H₂ S = 133. This point lies within the Ce₂ O₂ S phase field and at constant CO/CO₂ desulphurization with Ce₂ O₃ will take place up to point B. At point B, H₂ /H₂ S ≃ 10⁴ and the concentration of H₂ S is 0.004 vol. % (˜ 3 grains/100 ft.³). Beyond this point, desulphurization is not possible.

The basic theory for this invention is supported by the standard free energies of rare earth compounds likely to be involved. Examples of these appear in Table I which follows:

                                      TABLE 1                                      __________________________________________________________________________     Standard Free Energies of Formation of Some Rare Earth Compounds:              Δ6° = X-YT cal/g.f.w.                                                                                 Estimated                                  Reaction          X     Y    Temp.(° K).                                                                    Error(kcal)                                __________________________________________________________________________     CeO.sub.2(s) = Ce.sub.(1) + O.sub. 2(g)                                                          259,900                                                                              49.5 1071-2000                                                                             ± 3                                     Ce.sub.2 O.sub.3(s) = 2Ce.sub.(1) + 3/2 O.sub.2(g)                                               425,621                                                                              66.0 1071-2000                                                                             ± 3                                     La.sub.2 O.sub.3(s) = 2La.sub.(1) + 3/2 O.sub.2(g)                                               428,655                                                                              68.0 1193-2000                                                                             ± 3                                     CeS.sub.(s) = Ce.sub.(1) + 1/2 S.sub.2(g)                                                        132,480                                                                              24.9 1071-2000                                                                             ± 2                                     Ce.sub.3 S.sub.4(s) = 3Ce.sub.(1) + 2S.sub.2(g)                                                  483,180                                                                              98.2(*)                                                                             1071-2000                                                                             ± 10                                    Ce.sub.2 S.sub.3(s) = 2Ce.sub.(1) + 3/2 S.sub.2(g)                                               351,160(*)                                                                           76.0(*)                                                                             1071-2000                                                                             ± 10                                    LaS.sub.(s) = La.sub.(1) + 1/2 S.sub.2(g)                                                        123,250                                                                              25.3 1193-2000                                                                             ± 6                                     Ce.sub.2 O.sub.2 S.sub.(s)  = 2Ce.sub.(1) + 0.sub.2(g) + 1/2                                     410,730(g)                                                                           65.0 1071-2000                                                                             ± 15                                    La.sub.2 O.sub.2 S.sub.(s) = 2La.sub.(s) + O.sub.2(g) + 1/2                                      407,700(*)                                                                           65.0(*)                                                                             1193-2000                                                                             ± 15                                    __________________________________________________________________________      (*)Estimated                                                             

The three phase equilibria at 1273° K. for the Ce-O-S System is set out in Table II as follows:

                                      TABLE II                                     __________________________________________________________________________     Ce-O-S System                                                                  Three Phase Equilibria at 1273° K                                       REACTION            ΔG° cal                                                                    K.sub.1273                                        __________________________________________________________________________     Ce.sub.2 O.sub.3(s) + 1/2S.sub.2(g) = Ce.sub.2 O.sub.2 S.sub.(s) +             1/2O.sub.2(g)       14890 - 1.0T                                                                            (pO.sub.2 /pS.sub.2).sup.1/2 = 4.6 ×                                     10.sup.-3                                         Ce.sub.2 O.sub.2 S.sub.(s) + 1/2S.sub.2(g) = 2CeS.sub.(s)                                          145770 - 15.2T                                                                          pO.sub.2 /p.sup.1/2 S.sub.2 = 2.0 ×                                      10.sup.-22                                        3Ce.sub.2 O.sub.2 S.sub.(s) + 5/2 S.sub.2(g) = 2Ce.sub.3 S.sub.4(s) +          30.sub.2(g)         265830 + 1.4T                                                                           p.sup.3 O.sub.2 /p.sup.5/2 S.sub.2 = 1.1                                       × 10.sup.-46                                Ce.sub.2 O.sub.2 S.sub.(s) + S.sub.2(g) = Ce.sub.2 S.sub.3                                         59570 + 11.0T                                                                           pO.sub.2 /pS.sub.2 = 2.3 × 10.sup.-13       Ce.sub.3 S.sub.4(s) =  3CeS.sub.(s) + 1/2S.sub.2(g)                                                85740 - 23.5T                                                                           p.sup.1/2 S.sub.2 = 2.5 × 10.sup.-10        2Ce.sub.2 S.sub.3(s) = 2Ce.sub.3 S.sub.4(s) + 1/2S.sub.2(g)                                        87120 - 31.6T                                                                           p.sup.1/2 S.sub.2 = 8.9 × 10.sup.-8         CO.sub.(g) + 1/2O.sub.2(g) = CO.sub.2(g)                                                           - 67500 + 20.75T                                                                        pCO.sub.2 /(pCO . p.sup.1/2 O.sub.2) = 1.1                                     × 10.sup.7                                  H.sub.2(g) + 1/2S.sub.2(g) = H.sub.2 S.sub.(g)                                                     -21580 + 11.80T                                                                         pH.sub.2 S/(pH.sub.2 . p.sup.1/2 S.sub.2) =                                    13.4                                              H.sub.2(g) + 1/2O.sub.2(g) = H.sub.2 O.sub.(g)                                                     - 58900 + 13.1T                                                                         pH.sub.2 O/(pH.sub.2 . p.sup.1/2 O.sub.2) =                                    1.8 × 10.sup.7                              __________________________________________________________________________

Typical calculations of energy changes involved in the systems involved in this invention are as follows:

    __________________________________________________________________________     S.sub.2(g) + Ce.sub.2 O.sub.2 S.sub.(s) = Ce.sub.2 S.sub.3(s)                  + O.sub.2(g)                                                                   Ce.sub.2 S.sub.3(s) = 2Ce.sub.(l) + 3/2 S.sub.2(g) : ΔG° =        351160 - 76.0T cal                                                             Ce.sub.2 O.sub.2 S.sub.(s) = 2Ce.sub.(l) + O.sub.2(g) + 1/2 S.sub.2(g) :       ΔG° = 410730 - 65.0T cal                                          Ce.sub.2 O.sub.2 S.sub.(s) + S.sub.2(g) = Ce.sub.2 S.sub.3(s)                  + O.sub.2(g) : ΔG° = 59570 + 11.0T cal                            at 1273° K. ΔG° = 73573 cal and pO.sub.2 /pS.sub.2 =       2.33 × 10.sup.-13                                                        Ce.sub.2 O.sub.3(s) + 1/2 S.sub.2(g) = Ce.sub.2 O.sub.2 S + 1/2                O.sub.2(g)                                                                     Ce.sub.2 O.sub.3(s) = 2Ce.sub.(l) + 3/20.sub.2(g) : ΔG° =         425621 - 66.0T cal                                                             Ce.sub.2 O.sub.2 S.sub.(s) = 2Ce.sub.(l) + O.sub.2(g) + 1/2 S.sub.2(g) :       ΔG° = 410730 - 65.0T cal                                          Ce.sub.2 O.sub.3(s) + 1/2 S.sub.2(g) = Ce.sub.2 O.sub.2 S.sub.(s) + 1/2        O.sub.2(g) : ΔG° = 14891 - 1.0T cal                               at 1273° K. ΔG° = 13618 cal and (pO.sub.2 /pS.sub.2).s     up.1/2 = 4.6 × 10.sup.-3                                                 Ce.sub.2 O.sub.2 S.sub.(s) + 1/2 S.sub.2(g) = 2CeS.sub.(s) + O.sub.2(g)        Ce.sub.2 O.sub.2 S.sub.(s) = 2Ce.sub.(l) + 1/2 S.sub.2(g) + O.sub.2(g) :       ΔG° = 410730 - 65.0T cal                                          2CeS.sub.(s) = 2Ce.sub.(l) + S.sub.2(g) : ΔG° =264960 -           49.8T cal                                                                      Ce.sub.2 O.sub.2 S.sub.(s) + 1/2 S.sub.2(g) = 2CeS.sub.(s) + O.sub.2(g)        : ΔG° = 145770 - 15.2T cal                                        at 1273° K. ΔG° = 126420 cal. and pO.sub.2 /p.sup.1/2      S.sub.2 = 1.96 × 10.sup.-22                                              3Ce.sub.2 O.sub.2 S.sub.(s) + 5/2 S.sub.2(g) = 2Ce.sub.3 S.sub.4(s) + 3        O.sub.2(g)                                                                     2Ce.sub.3 S.sub.4(s) = 6Ce.sub.(l) + 4S.sub.2(g) : ΔG° =          966360 - 196.4T cal                                                            3Ce.sub.2 O.sub.2 S.sub.(s) = 6Ce.sub.(l) + 3 O.sub.2(g) + 3/2 S.sub.2(g)      : ΔG° = 1232190 - 195.0T cal                                      3Ce.sub.2 O.sub.2 S.sub.(s) + 5/2 S.sub.2(g) = 2Ce.sub.2 S.sub.4(s) + 3        O.sub.2(g) : ΔG° = 265830 + 1.4T cal                              at 1273° K. ΔG° = 267612 cal and p.sup.3 O.sub.2           /p.sup.5/2 S.sub.2 = 1.12 × 10.sup.-46                                   Ce.sub.3 S.sub.4(s) = 3CeS.sub. (s) + 1/2 S.sub.2(g)                           Ce.sub.3 S.sub.4(s) = 3Ce.sub.(l) + 2S.sub.3(g) : ΔG° =           48318 - 98.2T cal.                                                             3CeS.sub.(s) = 3Ce.sub.(l) + 3/2 S.sub.2(g) : ΔG° = 397,440       - 74.7T cal.                                                                   Ce.sub.3 S.sub.4(s) = 3CeS.sub.(s) + 1/2 S.sub.2(g) : ΔG° =       85740 - 23.5T cal.                                                             at 1273° K. ΔG° = 55824 cal p.sup.1/2 S.sub.2 = 2.6        × 10.sup.-10                                                             3Ce.sub.2 S.sub.3(s) = 2Ce.sub.3 S.sub.4(s) + 1/2 S.sub.2(g)                   2Ce.sub.3 S.sub.4(s) = 6Ce.sub.(l) + 4 S.sub.2(g) : ΔG° =         966360 - 196.4T cal.                                                           3Ce.sub.2 S.sub.3(s) = 6Ce.sub.(l) + 9/2 S.sub.2(g) : ΔG° =       1053480 - 228.0T cal.                                                          3Ce.sub.2 S.sub.3(s) = 2Ce.sub.3 S.sub.4(s) + 1/2 S.sub.2(g) :                 ΔG° = 87120 - 31.6T cal.                                          at 1273° K. ΔG° = 468893 cal. and p.sup.1/2 S.sub.2 =      8.9 × 10.sup.-9                                                          __________________________________________________________________________

    ______________________________________                                         H.sub.2(g) + 1/2 S.sub.2(g) = H.sub.2 S.sub.(g)                                H.sub.2(g) + 1/2 S.sub.2(g) = H.sub.2 S.sub.(g) : ΔG° =           -21580 + 11.80T cal.                                                           at 1273° K. ΔG° = -6559 and pH.sub.2 S/(pH.sub.2 .         p.sup.1/2 S.sub.2) = 13.4                                                             pH.sub.2 /pH.sub.2 S                                                                         log pS.sub.2                                                     1             - 2.25                                                           10.sup.2      - 6.25                                                           10.sup.4      -10.25                                                           10.sup.6      -14.25                                                           10.sup.8      -18.25                                                           10.sup.10     -22.25                                                           10.sup.12     -26.25                                                    ______________________________________                                    

    ______________________________________                                         H.sub.2(g) + 1/2 O.sub.2(g) = H.sub.2 O.sub.(g)                                H.sub.2(g) + 1/2 O.sub.2(g) = H.sub.2 O.sub.(g) : ΔG° =           -58900 + 13.1T cal.                                                            at 1273° K. ΔG° = -42223 cal. and                          (pH.sub.2 /pH.sub.2 O) p.sup.1/2 O.sub.2 = 5.6 × 10.sup.-8                      pH.sub.2 /pH.sub.2 O                                                                         log pO.sub.2                                                     10.sup.-4     - 6.5                                                            10.sup.-2     -10.5                                                            1             -14.5                                                            10.sup.2      -18.5                                                            10.sup.4      -22.5                                                            10.sup.6      -26.5                                                            10.sup.8      -30.5                                                     ______________________________________                                    

    ______________________________________                                         CO.sub.(g) + 1/2 O.sub.2(g) = CO.sub.2(g)                                      CO.sub.(g) + 1/2 O.sub.2(g) = CO.sub.2(g) : ΔG° = -67500 +        20.75T cal.                                                                    at 1273° K. ΔG° = - 41085 and pCO.sub.2 /(pCO.p.sup.1/     2 O.sub.2) = 1.1 × 10.sup.7                                                     pCO/pCO.sub.2 log pO.sub.2                                                     10.sup.-4     - 6.1                                                            10.sup.-2     -10.1                                                            1             -14.1                                                            10.sup.2      -18.1                                                            10.sup.4      -20.1                                                            10.sup.6      -24.1                                                            10.sup.8      -30.1                                                     ______________________________________                                    

In the foregoing general description of this invention, certain objects, purposes and advantages have been outlined. Other objects, purposes and advantages of this invention will be apparent, however, from the following description and the accompanying drawings in which:

FIG. 1 is a stability diagram showing w/o sulphur as partial pressure of CO;

FIGS. 2a and 2b show Ce₂ S₃ and Ce₂ O₂ S layers on a pellet of CeO₂ ;

FIG. 3 is a graph of the theoretical CeO₂ required for removal of 0.01 w/o S/THM;

FIG. 4 is a graph showing the volume of nitrogen required to produce a given partial pressure of CO;

FIG. 5 is a graph showing the CeO₂ requirements as a function of partial pressure of CO; and

FIG. 6 is a stability diagram for stack gas systems treated according to this invention.

Referring back to the discussion of free energy set out above, it is clear that these free energy changes may be used to determine the fields of stability of Ce₂ O₃, Ce₂ O₂ S, Ce₂ S₃, Ce₃ S₄ and CeS in terms of the partial pressure of Co and the Henrian sulphur activity of the melt at 1500° C. The resultant stability diagram is shown in FIG. 1, the boundaries between the phase fields being given by the following relationships:

    ______________________________________                                         BOUNDARY       EQUATION                                                        ______________________________________                                         Ce.sub.2 O.sub.3 - Ce.sub.2 O.sub.2 S                                                         log pCO = log h.sub.S + 3.53                                    Ce.sub.2 O.sub.2 S - Ce.sub.2 S.sub.3                                                         log pCO = log h.sub.S + 0.28                                    Ce.sub.2 O.sub.2 S - Ce.sub.3 S.sub.4                                                         log pCO = 0.83 log h.sub.S + 0.03                               Ce.sub.2 O.sub.2 S - Ces                                                                      log pCO = 0.5 log h.sub.S - 0.79                                Ce.sub.2 S.sub.3 - Ce.sub.3 S.sub.4                                                           log h.sub.S = - 1.47                                            Ce.sub.3 S.sub.4 - CeS                                                                        log h.sub.S = - 2.45                                            ______________________________________                                    

The phase fields in FIG. 1 are also shown in terms of the Henrian activity of oxygen, h_(O), and the approximate [w/o S] in the iron melt using an activity coefficient f_(S) ≃ 5.5 for graphite saturated conditions.

The coordinates of the points B, C, D and E on the diagram are given below:

    ______________________________________                                         Coordinates                                                                             B         C         D       E                                         ______________________________________                                         pCO atm. 9.8 × 10.sup.-3                                                                    6.5 × 10.sup.-2                                                                    1.0     1.0                                       h.sub.S  3.5 × 10.sup.-3                                                                    3.4 × 10.sup.-2                                                                    5.3 × 10.sup.-1                                                                  2.9 × 10.sup.-4                     Approx.  6.4 × 10.sup.-4                                                                    6.2 × 10.sup.-3                                                                    9.6 × 10.sup.-2                                                                  5.3 × 10.sup.-5                     [w/o S]                                                                        ______________________________________                                    

The points B and C represent simultaneous equilibria between the oxysulphide and two sulphides at 1500° C. These univariant points are only a function of temperature. The points E and D represent the minimum sulphur contents or activities at which oxysulphide and Ce₂ S₃ can be formed, respectively, at pCO = 1 atm. Thus, carbon saturated hot metal cannot be desulphurized by oxysulphide formation below h_(S) ≃ 2.9 × 10⁻⁴ ([w/o S] ≃ 5.3 × 10⁻⁵) at pCO = 1 atm. However, lower sulphur levels may be attained by reducing the partial pressure of CO.

The conversion of CeO₂ →Ce₂ O₃ →Ce₂ O₂ S→Ce₂ S₃ is illustrated in FIGS. 2a and 2b which show Ce₂ S₃ and Ce₂ O₂ S layers on a pellet of CeO₂ (which first transformed to Ce₂ O₃) on immersion in graphite saturated iron at ˜1600° C., initially containing 0.10 w/o S, for 10 hours. The final sulphur content was 18 0.03 w/o S and the experiment was carried out under argon, where pCO<<1 atm.

The conversion of the oxide to oxysulphide and sulphide is mass transfer controlled and, as in conventional external desulphurization with CaC₂, vigorous stirring will be required for the simple addition process and circulation of hot metal may be required in the `active` lining process.

From FIG. 1 it is apparent that the external desulphurization of graphite saturated iron is thermodynamically possible using RE oxides. For example the diagram indicates that hot metal sulphur levels of ˜0.5 ppm (point E) can be achieved by cerium oxide addition even at pCO = 1 atm. Desulphurization in this case will take place through the transformation sequence CeO₂ → Ce₂ O₃ → Ce₂ O₂ S which required 2 moles of CeO₂ to remove 1 gm. atom of sulphur. The efficiency of sulphur removal/lb. CeO₂ added can, however, be greatly increased by the formation of sulphides. 1 mole CeO₂ is required per g. atom of sulphur for CeS formation and 2/3 moles CeO₂ for Ce₂ S₃ formation. The theoretical CeO₂ requirements for the removal of 0.01 w/o S/THM for the various desulphurization products are given below and expressed graphically in FIG. 3.

    __________________________________________________________________________     PRODUCT                                                                               lb CeO.sub.2 /0.01 w/o S.THM                                                                ft.sup.3 CO/lb CeO.sub.2                                                               ft.sup.3 CO/0.01 w/o S.THM                         __________________________________________________________________________     Ce.sub.2 O.sub.2 S                                                                    2.15         2.1     4.5                                                CeS    1.1          4.2     4.5                                                Ce.sub.3 S.sub.4                                                                      0.8          4.2     3.4                                                Ce.sub.2 S.sub.3                                                                      0.7          4.2     3.0                                                __________________________________________________________________________

The volume of carbon monoxide produced in ft³ CO/lb CeO₂ and ft³ CO/0.01 w/o S.THM are also given in the above table for each desulphurization product. For efficient desulphurization the partial pressure of carbon monoxide should be sufficiently low to avoid oxysulphide formation. For example, FIG. 1 shows that oxysulphide will not form in a graphite saturated melt until [w/o S] < 0.01 when pCO ≃ 0.1 atm. It will form however when [w/o S] ≃ 0.10 at pCO = 1 atm. Thus by reducing the pCO in the desulphurization process to 0.1 atm., hot metal can be desulphurized to 0.01 w/o S with a CeO₂ addition of 0.72 lb/0.01 w/o S removed for each ton hot metal.

The choice of the method of reducing the partial pressure of carbon monoxide depends on economic and technical considerations. However, in an injection process calculations can be made for the volume of injection gas, say nitrogen, required to produce a given pCO. Thus:

    V.sub.N.sbsb.2 = V.sub.CO (1-pCO)/pCO

where

V_(co) is the scf of CO formed/lb CeO₂ added

V_(n).sbsb.2 is the scf of N₂ required/lb CeO₂ added and

pCO is the desired partial pressure of CO in atm.

The results of these calculations for Ce₂ S₃ formation are shown in FIG. 4, which also shows the [w/o S] in equilibrium with Ce₂ S₃(s) as a function of pCO. From this figure it is apparent that the volume of N₂ /lb CeO₂ required to form Ce₂ S₃ is excessive and if an injection process were used a balance would have to be struck between sulphide and oxysulphide formation. When, for example, hot metal is to desulphurize from 0.05 to 0.01 w/o S at pCO = 0.2 atm., ˜16 scf N₂ /lb CeO₂ would be required for Ce₂ S₃ formation and the sulphur content would drop to 0.02 w/o. The remaining 0.01 w/o S would be removed by oxysulphide formation. From FIG. 3, it can be seen that ˜2 lbs of CeO₂ /THM would be required for Ce₂ S₃ formation and 2 lbs for Ce₂ O₂ S formation giving a total requirement of 4 lbs CeO₂ /THM.

Calculations similar to the one above have been used to construct FIG. 5 where the CeO₂ requirements in lbs/THM are shown as a function of pCO.

When large volumes of nitrogen are used in an injection process the heat carried away by the nitrogen, as sensible heat, is not large but the increased losses by radiation may be excessive. Injection rates with CaC₂ for example are in the order of 0.1 scf N₂ /lb CaC₂.

Vacuum processing is an alternative method of reducing the partial pressure of carbon monoxide. This is impractical in hot metal external desulphurization but not in steelmaking (see below).

Still another alternative approach to external desulphurization using rare earth oxides is the use of active linings which would involve the `gunning` or flame-spraying of HM transfer car linings with rare earth oxides. Here the oxides would transform to oxysulphides during the transfer of hot metal from the blast furnace to the steelmaking plant, and the oxide would be regenerated by atmospheric oxidation when the car was emptied. It is estimated that for a 200 ton transfer car, conversion of a 2 mm layer (˜0.080") of oxide to oxysulphide would reduce the sulphur content of the hot metal by ˜0.02 w/o S. This process has the following advantages:

(1) continuous regeneration of rare earth oxide by atmospheric oxidation when the car is empty,

(2) reaction times would be in the order of hours,

(3) the absence of a sulphur rich desulphurization slag, and

(4) the absence of suspended sulphides in the hot metal.

The mechanical integrity and the life of an "active" lining is, of course, critical and some pollution problems may be associated with oxide regeneration by atmospheric oxidation.

With regard to steelmaking applications, vacuum desulphurization could be carried out by an "active" lining in the ASEA-SKF process and circulation vacuum degassing processes.

In the foregoing specification, we have set out certain preferred practices and embodiments of our invention, however, it will be understood that this invention may be otherwise embodied within the scope of the following claims. 

What is claimed is:
 1. A method of desulphurizing fluid materials comprising the steps of:(a) reacting a member from the group consisting of rare earth oxides, rare earth fluorocarbonates and rare earth oxyfluorides with sulphur to be removed from the fluid material at a sufficiently low oxygen potential to form one of the group consisting of rare earth sulphides and rare earth oxysulphides and mixtures thereof until a substantial portion of the sulfur has been reached, and (b) removing said oxysulphides and sulphides.
 2. The method of desulphurizing fluid materials as claimed in claim 1 wherein the rare earth oxides are reacted with sulphur.
 3. The method of desulphurizing fluid materials as claimed in claim 1 wherein Bastnasite concentrates are reacted with sulphur.
 4. The method of desulphurizing fluid materials as claimed in claim 1 wherein the oxygen potential is maintained at a low level by reducing the partial pressure of CO.
 5. The method of claim 4 wherein the partial pressure of CO is maintained below about 0.1 atmosphere.
 6. The method of desulphurizing fluid materials as claimed in claim 1 wherein rare earth oxide is added to the fluid material by injecting the rare earth oxide into the fluid material in a stream of inert gas sufficient to dilute carbon monoxide formed in the reaction of a level below about 0.1 atmosphere.
 7. The method of desulphurizing fluid material as claimed in claim 6 wherein the inert gas is nitrogen.
 8. The method of desulphurizing fluid material as claimed in claim 1 wherein rare earth oxide is added to said fluid material subject to a vacuum sufficient to maintain the partial pressure of carbon monoxide below about 0.1 atmosphere.
 9. The method of desulphurizing fluid material wherein the rare earth sulphide and oxysulphide is removed from the fluid material, regenerated with oxygen and returned to the fluid system for further desulphurization. 